SE179806C1 - Defoamer - Google Patents

Description

Inventors: C H Lighthipe, J Levy () eh A De Castro Priority requested by Iran on 13 June 1955 (USA) The present invention relates to a new and improved defoamer and more particularly to a new and improved defoamer which is particularly suitable for use in the paper industry.

Foaming was a serious problem in many industrial processes. Significant technical similarities thus arise in the production of pulp and paper, since some of the solutions and dispersions used in these processes have a tendency to skim. A large number of defoamers have been developed in the past to prevent or reduce the paperwork defects due to the foam pulping. Some of these funds have had significant progress at night. In some cases, however, it has been shown that they do not give their satisfactory result as yore unsatisfactory. The requirements for an effective defoamer for use in the paper industry are many and varied. The agent must be stable in acidic environments, because in many factories alum is usually added, ie. aluminum sulphate, to the pulp to assist in the formation of water-repellent paper by precipitation of an insoluble aluminum resinate on the fibers of the pulp. The addition of acidic aluminum sulfate often causes breakage of the emulsions of defoamer. Another requirement for defoamers for use in the paper industry is that the defoamers must be stable in the presence of various inorganic salts, since clays, carbonates and other fillers are usually added to the pulp in the manufacture of certain types of paper. Furthermore, the Mir foam vaporizer is delivered in such a form that it is easy to handle in the factory and Mit can be prepared for use in the manufacture of paper.

An object of the present invention is to provide a new and improved one defoamers. Another object of the invention is to provide a foam vaporizer which is suitable for scissors for use in the manufacture of pulp or popper. A further object of the invention is to provide a defoamer in the form of an anhydrous, readily emulsifiable solid product.

It has been found that the above-mentioned spirals can be filled with the defoamer of the present invention, which comprises a mixture of a normally solid, aliphatic, monohydric alcohol, and a normally solid, nonionic emulsifier. In certain embodiments, the novel agent of the present invention may also contain a normally solid, aliphatic acid and may have a precipitating alkaline agent. It has been found that such agents have excellent foaming properties, are very difficult to emulsify and can be produced in the form of solid, anhydrous products.

The normally solid aliphatic monohydric alcohol used in the preparation of the novel defoamer of the present invention is a matte aliphatic monohydric alcohol having a carbon chain of about 1422 carbon atoms. Alcohols of this type are solid at room temperature and at normal atmospheric pressure. The alcohols can be used alone or in the form of technical products, in which the alcohols are mixed with saturated fatty acids. Soul examples of this latter form may be mentioned the mixtures of saturated alcohol and saturated fatty acid which are obtained by straining a preheated, hydrogenated spermacetic oil. Such a mixture constitutes an inexpensive material containing the saturated fatty acids and saturated alcohols which are used in the defoamer of the present invention. Examples of suitable saturated alcohols which can be used in the defoamer are stearylal 2— - alcohol, cetyl alcohol, myristyl alcohol and the alcohols obtained from hydrogenated fats, such as hydrogenated fish oils, hydrogenated tallow, hydrogenated coconut oils and hydrogenated vegetable oils, such as peanut oil or cottonseed oil. The latter alcohols can be obtained from the corresponding glycerides according to customary technical procedures, such as catalytic hydrogenation at high temperature and high pressure of the corresponding glycerides or by sodium reduction of the corresponding glyceride in the presence of an alcohol, such as methyl-amyl alcohol. The alcohol component can make up about 50-90% by weight of the agent. Alcohol, however, suitably constitutes about 70-90% by weight of the final product.

In order to be suitable for use in the defoamer according to the present invention, the nonionic emulsifier must be a normal solid substance, i.e. have a melting point of at least about 40 ° C, and be an effective dispersant, i.e. the association must achieve an appropriate balance between hydrophobic and hydrophilic groups. The normally solid, nonionic emulsifier used in the compositions of the present invention is a condensation product of ethylene oxide and a hydroxy compound, such as an alkylated phenol or a high molecular weight alcohol. In these condensation products, the molar ratio of ethylene oxide to hydroxy purification can vary from a range of about 6 moles of ethylene oxide per 1 mole of hydroxy compound to about 40 moles of ethylene oxide per 1 mole of hydroxy. . Representative examples of the hydroxy compounds which can be used in the preparation of the condensation product in the emulsifier are alkylated phenols, such as isooctylphenol, and high molecular weight alcohols, such as stearyl alcohol, cetyl alcohol and those alcohols obtained from hydrogenated hydrogenated fats, tallow, hydrogenated coconut oil, and hydrogenated vegetable oils. The nonionic emulsifier usually constitutes about 10% of the final product. However, amounts of about 5-15% by weight of the emulsifier can be used.

The normally solid aliphatic acid, which is used in the preparation of the defoamer of the present invention, may be a flake matte aliphatic acid having a carbon chain of about 12-22 carbon atoms. Such acids are normally solidified at room temperature under normal atmospheric pressure.

The acids can be used as such or in admixture with saturated fatty alcohols, which are present in technical products prepared by cleavage of desalinated, hydrogenated spermacetic oil. Examples of suitable matte, aliphatic acids for inhalation in the defoamer of the present invention are lauric acid, myristic acid, palmitic acid, stearic acid and arachidonic acids. The fatty acid component which may be used may constitute about 10-40% of the weight of the agent. Normally it contains about 10-20% of the weight of the product.

The defoamers of the present invention may also contain as an ingredient a whitening alkaline material, such as sodium hydroxide, lialium hydroxide, amine, including alkanolamines, and the product obtained by reacting two moles of diethanolamine with one mole of stearic acid. For the composition of the present invention, it is especially preferred to use triethanolamine, and the product obtained by reacting 2 moles of diethanolamine with 1 mole of stearic acid. This material is usually used in an amount of about 10% by weight, although it is also possible to use larger or smaller amounts.

A particular advantage of the agent according to the invention is the ease with which it can be manufactured. The order in which the various constituents are mixed with each other does not in any way affect the physical or chemical properties of the final product. All the ingredients can be mixed with each other and placed on a suitable vessel, in which they are melted and mixed to form the final product. Alternatively, one or more of the constituents may first be transferred in liquid form, after which the remaining constituents are mixed in either simultaneously or sequentially. Regardless of the order in which the constituents are mixed, the mixing of the constituents is carried out by transferring the various substances to a liquid state, for example by passing the mixture at a temperature above the melting point of the most reactive material in a container provided with suitable heating means. In preparing the defoamer according to the present invention, the mixture of the various constituents must be stirred or mixed with another salt, so that the final product is certainly homogeneous. The heating and stirring are carried out continuously until the solution formed is uniform. The treatment to which the liquid mixture is then subjected depends on the physical form in which it is desired to obtain the defoamer. The mixture can thus be poured into light briar and the final product obtained in the form of a brick. The narrow mixture can also be atomized by spraying it through fine nozzles in countercurrent to a stream of cold air, whereby the foam vaporizer is obtained in the form of fine beads. The narrow mixture can also be led into a trough, by means of which a controlled amount of the mixture can be transferred to a cooled roll, for example cooled with saline circulating inside the roll, after which the solidified material is scraped off with a suitable place scraper knife, so that the product is obtained - —3 In the form of firm flakes. According to the preferred embodiment of the invention, the product is prepared in the form of flakes or beads, since such a product is very easy to emulsify, if used in such a form, and since it has been found that these forms are most suitable for transport and storage at paper mills. . The products are unmaltable under normal conditions regarding temperature and humidity and do not sinter together during transport and handling.

The defoamer of the present invention is supplied in the form of a solid, anhydrous product. This can be easily emulsified in the paper mill and diluted lampily, until the non-water constituents in the emulsion constitute about 0.25-1.0% by weight of the diluted emulsion, although even more evenly diluted emulsions can be used, for example with a concentration of 0.02-0.1%. The solid products of the present invention are very easy to disperse in water, with slight agitation at a temperature of about 1849 DEG C. sufficient to effect dispersion. This is a very significant advantage of the products of the present invention relative to previous defoamers, since in the use of these It is necessary to apply strong stirring and heating of the water to a temperature of at least 65 ° C. The diluted emulsions are suitably added to the pulp in such an amount that the non-water-containing materials in the foam evaporator are included in a content of about 1-5 parts per million parts or about 0.01-0.05% of the dry weight of the pulp in the suspension. The diluted emulsion can be added where needed and to any desired salt in a paper machine such as a Fourdrinier type or cylinder type machine, and effectively prevents the formation of undesirable foam under almost all operating conditions.

The invention will be further elucidated in the following with some examples. However, these examples are illustrative only and do not limit the scope of the invention. Parts refer to parts by weight.

Example 1. 40 parts of prefabricated and cleaved, hydrogenated spermacetic oil containing e: a higher fatty alcohols and 60% saturated fatty acids, 40 parts stearyl alcohol and 10 parts stearic acid were fused together and mixed intimately. While stirring was continued, 5 parts of a condensation product obtained by reacting 1 mole of isooctylphenol with 8.5 moles of ethylene oxide were added, together with 5 parts of triethanolamine. The narrow mixture was stirred until it was smooth and even. While still liquid, the mixture was passed to a chute, from which it was discharged onto a cooled roller. The film of material formed on the cooled roll cuts pades off with a knife. The product was obtained in the form of brittle, pale yellow flakes, which were Mita to disperse in water. The product proved to be a very effective defoamer both in the laboratory and in the manufacture of paper.

This defoamer was evaluated by testing its defoamer in synthetic white water (white water) having approximately the same composition as the white liquor used in a conventional paper machine. The white liquor was prepared by intimately mixing 99.111 parts of water, 0.089 parts of resin (the sodium resinate sold under the name Hercules XXX, Hercules Powder Company, Wilmington, Delaware), 0.005 parts of anhydrous calcium chloride, 0.493 parts of sodium silicate, 0.277 parts of anhydrous aluminum sulfate. 0.025 parts preservative. In the preparation of the white liquor, the alum content was varied to install the pH of the solution at 5.0. This foam evaporation test was carried out in a 1000 ml high bakery and fitted with a line on the side about 114 mm above the bottom. On one side near the bottom of the baker there was a side outlet, which by means of a rubber hose was connected to a centrifugal pump. This was used to continuously circulate the white liquor from the baker through the pump and through an outlet hose attached to the pump and back to the baker at such a speed that the solution remaining in the baker was hit by the re-entering solution with such force that foaming began. The aerating white liquor was reintroduced into the baker and struck the surface of the solution therein at an angle of 90 ° and occurred at a point about 75 mm above the surface of the solution.

In carrying out this prey, different solutions were tried. The first solution consisted of 500 ml of synthetic white liquor, pH 5.0, which did not contain any defoamer. The remaining solutions consisted of 500 ml of synthetic white liquor topped with 1 ml and 3 ml of a 0.25% emulsion of the product of this example. In carrying out these tests, the equal solutions are kept in the 1000 ml high baker, as described above. The surface of the solutions is approx. 32 mm below the marking 114 mm Above the bottom of the baker. The baker's side outlet is connected to the circulation pump by means of a rubber hose, after which the pump is started. Foam developed immediately in the baker. When judging the product's foam evaporation capacity on this salt, the time that Belot between the start of the pump and the time when the foam had risen to the mark 114 mm Above the baker's bottom was taken into account. When testing the solution of synthetic white liquor which did not contain any foam vapor When using the product according to the 10-religion example, the following result was obtained: when using 1 ml of 0.25% emulsion. 4— - The results of these tests clearly show that the product according to this example has an excellent ability to precipitate foam on synthetic white liquor.

To further prove the excellent defoaming properties of the product of Example 1, the exact same test was performed with a technical defoamer commonly used in papermaking. Using this defoamer, the following results were obtained: when using 1 ml of 0.25% emulsion, the foam had risen to the marked level after 68 seconds, while using 3 ml of the 0.25% emulsion had risen to the level of 0.25% emulsion. marked level after 181 s. A comparison of the results from the series of test experiments clearly shows that the product according to Example 1 constitutes a very effective defoamer, which is completely satisfactory for use in papermaking.

Example 2. 70 parts of stearyl alcohol and 20 parts of stearic acid were fused together, after which 10 parts of a condensation product of stearyl alcohol and ethylene oxide prepared by reacting ethylene oxide and stearyl alcohol were added to the narrow mixture in a ratio of 31.5 moles of ethylene oxide per mole of stearyl alcohol. The narrow mixture was stirred until it became clear and smooth, after which it was passed into a trough and transferred to flakes on a cooled roll as described in Example 1 to give a product in the form of a crust, white flakes which were easy to disperse in warm water.

The foaming ability of this product was evaluated in synthetic white liquor (pH 5.0) in the manner described in Example 1. It was found that with the addition of 1 ml of 0.25% emulsion of the product of Example 2, the foam rose to the marked level only after 70 seconds, while with the addition of 3 ml of the 0.25% emulsion of the product according to example 2 steps to the marked level only after 330 s and when adding 5 ml of 0.25% emulsion of the product according to example 2 steps to the marked level only after 540 s. When using synthetic white liquor, which did not contain any defoamer , the foam column rose to the marked level of 6 s. These results clearly show that the product according to Example 2 constitutes an excellent foam evaporator.

Example 3. The defoamer was prepared by melting and mixing 90 parts of stearyl alcohol and 10 parts of condensate of stearyl alcohol and ethylene oxide with a molar ratio of ethylene oxide to stearyl alcohol of 31.5: 1. The mixture was transferred to flakes on a cooled roll. The product was obtained in the form of sprouts, white flakes, which were easy to disperse in water.

The product's foam evaporation shape in Tetic white liquor (pH 5.0) was evaluated in the manner described in Example 1. It was found that when adding 1 ml of 25% emulsion of the product according to Example 3, the foam rose to the marked level only after 30 s, when adding 3 ml of the same emulsion rose to the marked level only after 250 s and at addition of 5 ml of the same emulsion only after 470 s. When using synthetic white liquor, which did not contain any defoamer, the buzzer rose to the marked level of 6 s. These results clearly show that the product of Example 3 is an excellent defoamer.

Example 4. A very effective defoamer was prepared by fusing 40 parts of split, hydrogenated spermacetyl oil, 40 parts of stearyl alcohol and 5 parts of stearic acid. To the narrow mixture were added 10 parts of amide ay stearic acid and diethanolamine prepared by reacting 2 moles of diethanolamine with 1 mole of stearic acid and 5 parts of a condensation product of stearyl alcohol and ethylene oxide, in which the molar ratio of stearyl alcohol to ethylene oxide is 1:14. clear and uniform in appearance. It was then cooled to room temperature and chopped on a drum dryer. The product was obtained in the form of sprouts, white flakes, which were allowed to disperse in water.

The product of Example 4 was tested in synthetic white liquor (pH 5.0) in the manner described in Example 1. It was found that the product of this example was as effective as the product of Example 1 in its foaming effect.

Example 5. 60 parts of hydrogenated fish oil alcohols, 30 parts of stearic acid and 10 parts of condensate of stearyl alcohol and ethylene oxide, in the milk molar ratio of ethylene oxide to stearyl alcohols 14: 1, were melted together and mixed until a uniform mixture was formed. The mixture is transferred to flakes on a cooled roller. The product was obtained in the form of spray, white flakes, which were easy to disperse in water.

The product of this example was judged on its ability to precipitate the foam on synthetic white liquor (pH 5.0) in the manner described in Example 1. The following results were obtained: yid addition of 1 ml of 0.25% emulsion of the product of this example, the foam rose to the marked level only after 95 s, while upon addition of 3 ml of the same emulsion the foam rose to the marked level only after 233 s When using synthetic white liquor, which did not contain any defoaming agent, the scrubber rose to the marked level in 10 seconds. These results clearly show that the product of this example is extremely satisfactory for precipitating the foam on synthetic white liquor.

Example 6. 80 parts of hydrogenated fish oil alcohols, 10 parts of stearic acid and 10 parts of - - the condensate of stearyl alcohol and ethylene oxide according to Example 2 was melted together and the mixture was stirred intimately until smooth. The mixture was transferred to flakes a cold waltz. The product was obtained in the form of spray, white flakes, which were easy to disperse in water.

The foaming properties of these products were tested in synthetic white liquor (pH 5.0) on the fabric described in Example 1. The following results were obtained: with the addition of 1 ml of 0.25% emulsion, the buzzer rose to the marked level only after 70 s, with the addition of 3 ml of the same solution only after 440 s and with the addition of 5 ml of the same emulsion only after 900 s. The foam produced in synthetic white liquor (pH 5.0), which joke contains some defoamer, reaches the marked level of 9 s. These results clearly show that the product of this example is an excellent defoamer.

Example 7. The product of this example was prepared in the same manner as that of the preceding example except that 80 parts of hydrogenated tallow alcohols were used instead of 80 parts of hydrogenated fish oil alcohols.

The foam vaporizing capacity of this product was evaluated in synthetic white liquor in the manner described in Example 1. The following results are obtained: with the addition of 1 ml of 0.25% emulsion the foam rose to the marked level only after 80 s, with the addition of 3 ml of the same emulsion only after 300 s and with the addition of 5 ml of the same emulsion only after 510 s. The foam, which is produced in synthetic white liquor (pH 5.0) which joke contains some defoamer, reached the marked level ph 9 s. These results clearly show that the product according to this example also has excellent defoaming properties.

Example 8. 62.5 parts of hydrogenated fish oil alcohols, 32.5 parts of stearic acid and 5 parts of condensation product of stearyl alcohol and ethylene oxide, in which the molar ratio of ethylene oxide to stearyl alcohol of 31.5: 1, were melted together and mixed until the mixture was uniform. The product was then planed on a cooled roller and collected in the form of cracked, white flakes. The product was easy to disperse in hot water and when judging its foam vaporizing form in the manner described in Example 1, it was found that the product had a very strong form of suppressing foam in synthetic white liquor.

Example 9. 57.5 parts of hydrogenated fish oil alcohols, 27.5 parts of stearic acid and 15 parts of the condensate of stearyl alcohol and ethylene oxide used according to Example 8 were filtered together and mixed until the mixture was even. The product was then planed on a cooled roll and collected in the form of bright white flakes. The product was easy to disperse in hot water and appeared on judging its foam vaporizing form ph the method described in Example 1 be effective for depressurizing the foam in synthetic white liquor.

Claims (14)

Patent claim: A solid defoamer containing about 50-90% by weight of a matte aliphatic monohydric alcohol having a carbon chain having about 14-22 carbon atoms, about 0-40% by weight of an aliphatic matte monocarboxylic acid having a carbon chain of about 12-22 carbon atoms, about 5-15% by weight of a normal solid, nonionic, surfactant and about 0% alkaline, whitening material. 2. An agent according to claim 1, characterized in that it contains about 70-80% by weight of the matt aliphatic monohydric alcohol, about 10-30% by weight of the matt aliphatic monocarboxylic acid and about 5-15% by weight. of the normally solid nonionic surfactant. Agent according to claim 1, characterized in that it contains about 90% by weight of the matte, aliphatic monohydric alcohol and about 10% of the normally solid, nonionic, surfactant. Agent according to claim 3, characterized in that the alcohol is stearyl alcohol. Agent according to claim 4, characterized in that the nonionic emulsifier consists of a solid condensation product of ethylene oxide and stearyl alcohol. Agent according to claim 5, characterized in that the solid condensation product of ethylene oxide and stearyl alcohol has been prepared by reacting ethylene oxide and stearyl alcohol in a molar ratio of about 31.5: 1. Agent according to claim 2, characterized in that the normally solid, nonionic, surfactant is a solid condensation product of ethylene oxide and stearyl alcohol. Agent according to claim 7, characterized in that the alcohol consists of stearyl alcohols and that the acid consists of stearic acid. 9. An agent according to claim 1, characterized in that it contains about 70 parts by weight of stearyl alcohol, about 20 parts by weight of stearic acid and about 10 parts by weight of a condensation product prepared by fusing ay 1 mole of stearyl alcohol with about 31 parts. 5 moles of ethylene oxide. 10. An agent according to claim 1, characterized in that it contains about 70-80% by weight of the matte, aliphatic, monohydric alcohol, about 10-30% ay of the matte, aliphatic acid, about 5-15% of the nonionic surfactant and about 10% by weight of the alkaline, whey-forming material. 6 --- t79806 - Agent according to claim 10, characterized in that the normally solid, nonionic emulsifier consists of a solid condensation product of isooctylphenol and ethylene oxide and in which the alkaline whitening material consists of triethanolamine. Agent according to claim 10, characterized in that the normally solid, nonionic emulsifier consists of a solid condensation product of stearyl alcohol and ethylene oxide and that the alkaline, whey-forming material is a condensation product obtained by reacting about 2 moles of diethanolamine with stearic acid. 13. An agent according to claim 1, Urinary characterized in that it contains about 40 parts by weight of presalted and cleaved, hydrogenated spermacetyl oil, about 40 parts by weight of stearyl alcohol, about 10 parts by weight of stearic acid, about 10 parts by weight of a condensation product obtained by on the addition of about 8.5 moles of ethylene oxide with 1 mole of isooctylphenol, and about 5 parts by weight of triethanolamine. 14. An agent according to claim 1, Urinary characterized in that it contains about 40 parts by weight of desalinated and cleaved, hydrogenated spermacetyl a, about 40 parts by weight of stearyl alcohol, about 5 parts by weight of stearic acid, about 10 parts by weight of a condensation product produced by reacting about 2 moles of diethanolamine with 1 mole of stearic acid, and about 5 parts by weight of a condensation product obtained by reacting 1 mole of stearyl alcohol with about 31.5 moles of ethylene oxide. Cited publications: Patents (from France 1 018 241. Stockholm 1962. Kungl. Bokir. P. A. Norstedt & Semen 620089